Production of methanol and other carbon compounds and catalytic agents for use therein



Patented Nov. 17, 1936 UNITED STATES 2,061,470 PRODUCTION OFMETHANOL ANDornnn CAR.

BON COMPOUNDS AND CATALYTIC AGENTS FOR USE THEREIN Alfred T. Larson,Wilmington, Del), assignor to E. I. du Pont de Nemours & Company,Wilmington, Del., a corporation of Delaware No Drawing. ApplicationNovember 16, 1933,

Serial No. 698,315

9 Claims. (01.260-156) -1( It is known that oxygenated hydrocarbons, and

particularly methanol and its homologues, may

be prepared synthetically by passing a gaseous mixture containing carbonmonoxide and hydrogen under pressure over a catalyst. The syn- 5 thesisdepends upon reactions of which the following for methanol ischaracteristic:

In my n. s. Patent No. 1,844,129 1 have dea scribed a process formanufacturing oxygenated hydrocarbons and especially methanol, theprocess involving the use-of catalysts prepared by fusing andsubsequently reducing a mixture of copper oxide and manganese oxide.

It is the object of the present invention to provide a furtherimprovement in the process described ln the aforementioned patent.

Other objects and advantages will be-apparent as the invention is betterunderstood by refer- 30 ence to the following specification in which itspreferred embodiments are described;

I have discovered thatimproved results may be obtained in carrying outreactions in thegaseous phase in the presence of a catalyst consistingota reduction product of a fused mixture of copper oxide and manganeseoxide, or copper oxide and since oxide, if there is incorporated in saidcatalysts one or. more of the elements magnesium, aluminum, chromiumzirconium, vanadium, 40 titanium, thorium, silicon and cerium.

The catalysts herein described exhibit an activity superior to that of acatalyst consisting of fused and reduced copper oxide and manganese.

oxide alone; andalso superior to that of any of 45 the foregoing list ofelements taken singly-orin combination with each other. The term"superior activity" is used to indicate that with a given rate of gasflow the catalysts give a higher yield of. product per hour or,correspondingly, to attain a given hourly production a lower rate of gasfiow'may be maintained.

-In carrying'out the invention the prepared catalyst is disposed inasuitable receptacle adaptt ed to withstand the pressure at which the re-55 action is conducted. Thegaseous mixturev is introduced at the propertemperature which may be regulated and maintained in any desired way.The gaseous mixture containing the product of the reaction is withdrawn"and cooled to efiect condensation of the productor is treated otherwisefor the recovery thereof.

The catalysts are particularly well adapted for the synthesis ofmethanol from gaseous mixtures containing hydrogen and carbon monoxide.This reaction may be conducted with the described cat- 10 alysts atvarious pressuresand temperatures, but I prefer to carry out thesynthesis of methanol at a pressure within the range of 400 to 1000atmospheres and at a temperature of 250 to 500 C. The usefulness ofthe'catalysts is not limited to the treatment of gaseous mixtures of anyparticular composition, it being possible to efiect the synthesis ofmethanol, for example, with the improved catalysts by introducinggaseous mixtures containing hydrogen and carbon monoxide in which theproportion of the latter is relatively low, for example, between 3 and15%. It the gaseous mixtures contain relatively higher proportions ofcarbon monoxide; the reaction proceeds more vigorously, greaterquantities of heat are evolved and corresponding provision must be made,therefore, for the dissipation of heat so that the catalysts may not bedamaged by overheating and undesirable side reactions, such asmethanation, maybe avoided. i

The following exampies will serve to indicate the preferred procedure inpreparing and utilizing catalysts such as are described herein, it beingunderstood, howevenvthat the invention is not limited tothe details ofoperation or the particular conditions as set forth.

Example 1.--Prepare an intimate mixture of seventy-five-parts by weightof pure cupric oxide,

' twenty parts of j pure manganese dioxide and .The catalyst th'u'sprepared may be employed for the production of methanol by passing agaseous mixture containing hydrogen and carbon monoxide in the volume,ratio of twenty to one at a space velocity of 100,000 to 150,000, apressure of 900 atmospheres and while maintaining a temperature withintherange of 250 to 400 C. The.

' principal product is methanol, which associcombination with copper andmanganese can beprepared similarly by combining the oxides of Example4.-Eighty-two parts of pure cupric oxide, fifteenparts of pure manganesedioxide and three parts of pure zirconium oxide.

Example 5.-Eighty-five parts of pure cupric oxide, ten parts of puremanganese dioxide and five parts of pure vanadium oxide.

Example 6.Eighty-seven parts of pure cupric oxide, ten parts of puremanganese dioxide and three parts pure titanium oxide.

Example 7.Seventy-eight; parts of pure cupr/ic oxide, twenty parts ofpure manganese'dioxide and two parts of pure thorium oxide.

Example 8.fiSeventy-five' parts of pure cupric oxide, twenty. parts ofpure manganese dioxide and five parts or pure silica.

Example 9. Seventy-nine parts of pure cupric oxide, twenty parts of puremanganese dioxide and one part of pure cerium oxide.

Example 10.-Eighty-seven parts of. pure copper oxide, ten parts of purezinc oxide, and three parts of aluminum oxide.

Example 11.Eighty-flve parts of copper oxide, ten parts of zinc oxide,diumoxide.

Example 12.Eighty parts copper oxide, fifteen parts manganese oxide, 2.5parts magnesium oxide, and 2.5 parts chromium oxide.

Example 1'3. Seventy-five parts copper oxide, twenty parts of manganeseoxide, 25 parts magnesium oxide, and 2.5 parts vanadium oxide.

The catalysts described may be used in the synthesis of methanolhydrocarbons and for conducting other reactions in the gaseous phase ina similar manner under conditions of pressure and temperature that mayvary within a wide range, depending upon the particular nature of thedesired reaction. and of the product to be 'prepared.. A catalystcontaining two or more of the elements mentioned in these elements- Suchcatalysts Have the desirable characteristics hereinbefore mentioned andmay beutilized in efiecting various reactions in the gaseous phaseincluding the production of oxygenated hydrocarbons such as methanol.

It is to be understood that while the gaseous,

mixtures employed need not-be limited to those Y containing hydrogen andcarbon monoxide exclusively, the gases should, nevertheless, be freedfrom impurities which are likely to deleteriously affect thec'atalyst,-and of these the'compounds of sulphur are the most commonlyencountered.

, The. sulphur compounds may be removed preliminarily from the gases bysuitable treatment thereof in accordance witli the well understoodpractice. In'synthesizing methanol and the like,

it is recommended-that suitable precautions be taken'for avoiding thepresence of metals of the iron group (iron, nickel, .and cobalt) in thecatalyst and'in the gases that are to react.

and five parts of vanaand other oxygenated :magnesium,

20% manganese oxide, an

I have no theory or explanation to offer for any changes which may occurin the composition of the catalysts. during either their reduction oractual use. It may be that in some cases the reduction yields a lowerand especially active oxide which in conjunction with the activatedcopper with which it is associated forms a mass peculiarly adapted forthe catalytic production of oxygenated hydrocarbons. In any event, it isto be understood that the term catalyst as employed in the claimsincludes the contact mass in the form in which it may occur during itsuse.

It will be apparent from the foregoing that by providing new catalystsof superioractivity and improved physical form, decreasing catalystconsumption and improving smoothness of operation, and by thusfacilitating the production of oxygenated hydrocarbons and otherdesirable products of synthetic and other reactions, the presentinvention represents a distinct advance in the art. While the inventionhas been describedmore particularly with reference to the synthesis ofmethanol, the improved catalysts and the process may be utilized .withsimilar advantages in conducting other reactions in the gaseous phase.

The various details of apparatus and procedure may be modified to meetthe particular conditions of the reaction, the products being recoveredin any suitable or desirable way, it

being possible in the synthesis of methanol, for example, at pressuresabove 200 atmospheres to practically completely condense methanol fromthe gases by cooling with water. at ordinary temperature. The methanolcan be separated otherwise and other products can be treated in themanner, best adapted to e'ifect the separation thereof in an economicaland satisfactory way.

Various changes may be made in the details of operation hereinbeforedescribed without departing from the inventionorsacrificing any of theadvantages thereof. I-claim:

1. The improved catalyst for reactions in the gaseous phasecomprising-the reduction product of a fused mixture containing from 1 to5% of an oxide of an'element of the group consisting of chromium,vanadium, zirconium,- aluminum, magneslum, titanium, thorium, siliconand cerium, and from 97 to 95% of copper oxide, and

manganese oxide,-the copper oxide being in I excess.

2. The improved catalyst for reactions in the gaseous phasecomprising'the reduction product of a fused mixture containing from 1 to5% of' an oxide of an element of the group consisting of chromium,vanadium, zirconium, aluminum, titanium, thorium, silicon and cerium,and from 75 to 87% copper oxide and from 20- to 10% manganese oxide.

3. The improved catalyst for reactions in the.

gaseous phase comprising the reduction product of a fused mixturecontaining 80% copper oxide,

15% manganese oxide, and'5% chromium oxide.

4. The improved catalyst for reactions in the of a f 'd mixturecontaining 82% copper oxide, 15% manganese oxide, aid 3% vanadium oxide.

phase comprising the reduction product 5. The improved catalyst forreactions in the gaseous phase comprising the reduction product of afused mixture containing 79% copper oxide,

0 cerium oxide! 6. The process ofsynthesizing oxygenated organiccompounds which comprises subjecting a gaseous mixture containinghydrogen and an L t v 2,001,470

copper oxide and from 20 to 10% manganese oxide of carbon to a catalystat an elevated temperature and pressure, saiiLcataiyst comprising thereduction product of a fused mixture containing fromul to 5% of an oxideof an element of the group consisting of chromium, vanadium, zirconium,aluminum, magnesium, titanium, thorium, silicon, and cerium, and from 97to 95% y i of copper oxide and manganese oxide, the coppe oxide being inexcess.

'7. The process of synthesizing oxygenated organic compounds whichcomprises subjecting a of the group consisting or chromium, vanadium,aluminum, magnesium, titanium, thorium, silicon, andcerium, and from 75to 87% zirconium,

oxide.

8. The process oi. synthesizing oxygenated organic compounds whichcomprises subjecting a gaseous mixture containing .hydrogen and an oxideof carbon to a catalyst at an elevated temperature and pressure, saidcatalyst comprising oxide of carbon to a catalyst at an elevated temperature and pressure, said catalyst comprising,

. the reduction product of a fused mixture containing 82% copper oxide,15% manganese oxide and 3%;vanadium oxide.

- '1. LARSON.

